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Pressure-Induced Solidification of 1-Butyl-3-methylimidazolium Tetrafluoroborate

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Abstract

We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]+ cation. We have found that liquid [bmim][BF4] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]+ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF4]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid.

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Authors and Affiliations

  1. Department of Applied Chemistry, National Defense Academy, 1-10-20, Hashirimizu, Yokosuka, Kanagawa, 239-8686, Japan

    Machiko Shigemi, Takahiro Takekiyo & Yukihiro Yoshimura

  2. Department of Materials Science and Engineering, National Defense Academy, 1-10-20, Hashirimizu, Yokosuka, Kanagawa, 239-8686, Japan

    Hiroshi Abe

  3. Graduate School of Humanities and Sciences, Ochanomizu University, 1-1-2 Otsuka, Tokyo, 112-8610, Japan

    Nozomu Hamaya

Authors
  1. Machiko Shigemi
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  2. Takahiro Takekiyo
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  3. Hiroshi Abe
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  4. Nozomu Hamaya
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  5. Yukihiro Yoshimura
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Correspondence to Yukihiro Yoshimura.

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Shigemi, M., Takekiyo, T., Abe, H. et al. Pressure-Induced Solidification of 1-Butyl-3-methylimidazolium Tetrafluoroborate. J Solution Chem 43, 1614–1624 (2014). https://doi.org/10.1007/s10953-014-0233-9

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  • DOI: https://doi.org/10.1007/s10953-014-0233-9

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